EP3263619A1 - Alkoxysilane and allophanate functionalised coating agent - Google Patents

Abstract

The present invention relates to alkoxysilane and allophanate functionalized coating compositions, a process for their preparation, and their use.

Description

The present invention relates to alkoxysilane and allophanate functionalized coating compositions, a process for their preparation, and their use.

Polyurethanes have proven to be high quality building blocks for paint, adhesive, sealant and plastic systems for many decades. In this case, additional alkoxysilane groups here an important role z. In terms of network density, chemical resistance and scratch resistance, primarily through the formation of siloxane and polysiloxane structures.

Molecules which have both alkoxysilane groups and isocyanate groups offer the possibility of incorporating the components resulting in the reaction products, siloxanes and polyurethane groups, through one component. Even such substances have long been in use, for. In the form of isocyanatoalkyltrialkoxysilanes.

Alkoxysilane-terminated polyurethanes prepared from isocyanatoalkyltrialkoxysilanes and alcohols are likewise known and are used, for example, for the preparation of highly crosslinked, hard coating compositions (eg EP2676982A1 ) used. In the EP2676982A1 described alkoxysilane-containing coating compositions are disadvantageous because they have only short pot lives.

Allophanate-containing binders are known. Alkoxysilane-functionalized allophanates are also known. Here, different types are to be distinguished, which are shown below, but do not correspond to the structure or the use in the alkoxysilane-functionalized allophanates according to the invention contained in the alkoxysilane and allophanate-functionalized binder.

So the in WO2008 / 043722 allophanates III (1) obtained by reacting NCO-terminated allophanate-containing polyurethanes I (1) with isocyanate-reactive alkoxysilanes II (1) (eg aminoalkyltrialkoxysilane). The allophanate groups are thus located in the center of the polyurethane chain and the alkoxysilane function is attached via the terminal isocyanate group in the context of a urea function (structure III (1), equation 1).

DE102005041953 describes the reaction of a polyol I (2) with an average molecular weight of 3000-20000 g / mol with an excess of isocyanatopropyltrimethoxysilane II (2), so that it forms an allophanate IV (2) with two after polyurethane formation III (2) Alkoxysilane functions per allophanate unit comes.

In DE102005041954 Is a polyurethane I (3) with isocyanatopropyltrimethoxysilane II (3) and heated until allophanate structures form. In this case, the alkoxysilane group is grown on the terminal nitrogen of allophanate group III (3) (Equation 3).

J. Kozakiewicz et al. published in Progress in Organic Coatings 72 (2011) 120-130 the reaction of isocyanatopropyltrimethoxysilane I (4) with methanol to give the corresponding urethane II (4) and then with hexamethylene diisocyanate trimer III (4). In the resulting highly viscous allophanate IV (4), the alkoxysilane function is attached to the tertiary, central amine of the allophanate group (Equation 4).

The allophanate function is used in the application described as a blocking agent for the hexamethylene diisocyanate trimer, which was used as a crosslinker for hydroxy-functionalized polyester polyols.

There is also a need today for new silane-containing coating compositions which have special properties.

The object of this invention was to make available novel silane-containing coating compositions which are suitable for the development of highly crosslinked, hard and nevertheless flexible coatings and which are distinguished by an extended pot life.

This object is achieved by alkoxysilane and allophanate-functionalized coating compositions according to the present invention.

Surprisingly, it has been found that the alkoxysilane-functionalized allophanate-containing coating compositions according to the invention are suitable for use as paint, adhesive or sealant. In particular, the alkoxysilane and allophanate-functionalized coating compositions according to the invention can be used for the development of highly crosslinked, particularly hard coatings with high flexibility. In addition, the novel alkoxysilane and allophanate-functionalized coating compositions which comprise the binder component a) according to the invention, which is an alkoxysilane- and allophanate-functionalized urethane, are distinguished by a long pot life.

1. a) 10-99 Gew.-% wenigstens einer Bindemittelkomponente aus dem Reaktionsprodukt von
   1. I.
      1. A) Alkoxysilangruppen haltige Monourethane A) der Formel 1
         
                  R_n (OR¹)_3-n Si-R²-NH-(C=O)-OR³     Formel 1
         
         wobei R_n, R¹, R² und R³ unabhängig voneinander Kohlenwasserstoffreste mit 1-8 C-Atomen bedeuten, wobei diese linear, verzweigt oder cyclisch sein können, oder auch cyclisch ineinander übergehen können, und n gleich 0-2 bedeutet,
         und
      2. B) mindestens einem Diisocyanat B),
         optional in Gegenwart mindestens eines Katalysators K),
         in einem Mol-Verhältnis von A) zu B) von 1,0: 1,5 bis 1,0 : 0,6, bevorzugt 1,15 : 1 bis 0,85 : 1, besonders bevorzugt von 1 : 1.
   2. II. und der anschließenden Umsetzung
      • C) mit mindestens einem Diol und/oder Polyol C),
      optional in Gegenwart mindestens eines Katalysators K),
      im Verhältnis der NCO-Gruppen des Reaktionsprodukts I. zu den OH-Gruppen des Diols und/oder Polyols II. C) von 1,0 : 1,5 bis 1,0 : 0,6, bevorzugt 1,15 : 1 bis 0,85 : 1, besonders bevorzugt 1 : 1,
2. b) 1-90 Gew.-% wenigstens eine Bindemittelkomponente, bevorzugt ein hydroxylgruppenhaltiges oder amingruppenhaltiges Bindemittel,
3. c) 0-50 Gew.-% wenigstens ein aromatisches, aliphatisches oder cycloaliphatisches Polyisocyanat, das eine NCO-Funktionalität von wenigstens 2, bevorzugt 2,8 bis 6 aufweist,
4. d) 0-5 Gew.-% wenigstens einen Katalysator,

wobei sich die Komponenten a)-d) zu 100 Gew.-% addieren,

• e) optional Hilfsstoffstoffe und/oder Zusatzstoff,
• f) optional Lösungsmittel.

The invention relates to alkoxysilane-functionalized and allophanate-functionalized coating compositions containing

1. a) 10-99 wt .-% of at least one binder component from the reaction product of
   1. I.
      1. A) alkoxysilane-containing monourethanes A) of the formula 1
         
         R _n (OR ¹ ) _3-n Si-R ² -NH- (C = O) -OR ³ Formula 1
         
         wherein R _n , R ¹ , R ² and R ³ independently of one another are hydrocarbon radicals having 1-8 C atoms, which may be linear, branched or cyclic, or may also merge cyclically into one another, and n is 0-2,
         and
      2. B) at least one diisocyanate B),
         optionally in the presence of at least one catalyst K),
         in a molar ratio of A) to B) of 1.0: 1.5 to 1.0: 0.6, preferably 1.15: 1 to 0.85: 1, particularly preferably 1: 1.
   2. II. And the subsequent implementation
      • C) with at least one diol and / or polyol C),
      optionally in the presence of at least one catalyst K),
      in the ratio of the NCO groups of the reaction product I to the OH groups of the diol and / or polyol II. C) of 1.0: 1.5 to 1.0: 0.6, preferably 1.15: 1 to 0 , 85: 1, more preferably 1: 1,
2. b) 1-90% by weight of at least one binder component, preferably a hydroxyl-containing or amine-group-containing binder,
3. c) 0-50% by weight of at least one aromatic, aliphatic or cycloaliphatic polyisocyanate which has an NCO functionality of at least 2, preferably 2.8 to 6,
4. d) 0-5% by weight of at least one catalyst,

wherein components a) -d) add up to 100% by weight,

• e) optional excipients and / or additive,
• f) optional solvent.

1. a) 10-99 Gew.-% wenigstens einer Bindemittelkomponente aus dem Reaktionsprodukt von
   1. I.
      1. A) Alkoxysilangruppen haltige Monourethane A) der Formel 1
         
                  R_n (OR¹)_3-n Si-R²-NH-(C=O)-OR³     Formel 1
         
         wobei R_n, R¹, R² und R³ unabhängig voneinander Kohlenwasserstoffreste mit 1-8 C-Atomen bedeuten, wobei diese linear, verzweigt oder cyclisch sein können, oder auch cyclisch ineinander übergehen können, und n gleich 0-2 bedeutet,
         und
      2. B) mindestens einem Diisocyanat B),
         optional in Gegenwart mindestens eines Katalysators K),
         in einem Mol-Verhältnis von A) zu B) von 1,0 : 1,5 bis 1,0 : 0,6, bevorzugt 1,15 : 1 bis 0,85 : 1, besonders bevorzugt von 1 : 1.
   2. II. und der anschließenden Umsetzung
      • C) mit mindestens einem Diol und/oder Polyol C),
      optional in Gegenwart mindestens eines Katalysators K),
      im Verhältnis der NCO-Gruppen des Reaktionsprodukts I. zu den OH-Gruppen des Diols und/oder Polyols II. C) von 1,0 : 1,5 bis 1,0 : 0,6, bevorzugt 1,15 : 1 bis 0,85 : 1, besonders bevorzugt 1 : 1;
2. b) 1-90 Gew.-% wenigstens eine Bindemittelkomponente, bevorzugt ein hydroxylgruppenhaltiges oder amingruppenhaltiges Bindemittel,
3. c) 0-50 Gew.-% wenigstens ein aromatisches, aliphatisches oder cycloaliphatisches Polyisocyanat, das eine NCO-Funktionalität von wenigstens 2, bevorzugt 2,8 bis 6 aufweist,
4. d) 0-5 Gew.-% wenigstens einen Katalysator,

wobei sich die Komponenten a)-d) zu 100 Gew.-% addieren,

• e) optional Hilfsstoffstoffe und/oder Zusatzstoff,
• f) optional Lösungsmittel.

The invention relates to alkoxysilane-functionalized and allophanate-functionalized coating compositions consisting of

1. a) 10-99 wt .-% of at least one binder component from the reaction product of
   1. I.
      1. A) alkoxysilane-containing monourethanes A) of the formula 1
         
         R _n (OR ¹ ) _3-n Si-R ² -NH- (C = O) -OR ³ Formula 1
         
         wherein R _n , R ¹ , R ² and R ³ independently of one another are hydrocarbon radicals having 1-8 C atoms, which may be linear, branched or cyclic, or may also merge cyclically into one another, and n is 0-2,
         and
      2. B) at least one diisocyanate B),
         optionally in the presence of at least one catalyst K),
         in a molar ratio of A) to B) of 1.0: 1.5 to 1.0: 0.6, preferably 1.15: 1 to 0.85: 1, particularly preferably 1: 1.
   2. II. And the subsequent implementation
      • C) with at least one diol and / or polyol C),
      optionally in the presence of at least one catalyst K),
      in the ratio of the NCO groups of the reaction product I to the OH groups of the diol and / or polyol II. C) of 1.0: 1.5 to 1.0: 0.6, preferably 1.15: 1 to 0 , 85: 1, more preferably 1: 1;
2. b) 1-90% by weight of at least one binder component, preferably a hydroxyl-containing or amine-group-containing binder,
3. c) 0-50% by weight of at least one aromatic, aliphatic or cycloaliphatic polyisocyanate which has an NCO functionality of at least 2, preferably 2.8 to 6,
4. d) 0-5% by weight of at least one catalyst,

wherein components a) -d) add up to 100% by weight,

• e) optional excipients and / or additive,
• f) optional solvent.

R _n , R ¹ , R ² and R ³ are preferably simultaneously or independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, or tert-butyl.
Preferably, n = 0.
R ¹ and R ³ are preferably simultaneously or independently of one another methyl or ethyl.
R ² is preferably methyl or propyl.
Preferably, compounds with n equal to 0, R ¹ and R ^{3 are} simultaneously or independently of one another identical to methyl or ethyl, and R ² simultaneously or independently of one another is methyl or propyl.
Preferably, R ³ = R ¹ .
Preference is given to compounds with n equal to 0 and R ² being methyl or propyl, and R ¹ being methyl or ethyl and R ³ = R ¹ .

Most preferably, the compound n is 0, R ¹ and R ³ are methyl and R ² is propyl, N-Trimethoxysilylpropylmethylcarbamat.

The diisocyanate B) used according to the invention may be any desired aromatic, aliphatic, cycloaliphatic and / or (cyclo) aliphatic diisocyanate. In a preferred embodiment, the term "(cyclo) aliphatic diisocyanate" as used herein means that NCO groups simultaneously attached to a ring and NCO groups attached to an aliphatic radical are present in a molecule, as e.g. B. isophorone diisocyanate is the case. In a preferred embodiment, the term "cycloaliphatic diisocyanate" as used herein means a diisocyanate having only NCO groups directly attached to the cycloaliphatic ring, e.g. B. diisocyanatodicyclohexylmethane (H12MDI).

As aromatic diisocyanates B), in principle, all known aromatic compounds are suitable. Particularly suitable are 1,3- and 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, 2,6-tolylene diisocyanate (2,6-TDI), 2,4-tolylene diisocyanate (2,4-TDI), 2, 4'-diphenylmethane diisocyanate (2,4'-MDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), the mixtures of monomeric diphenylmethane diisocyanates (MDI) and oligomeric diphenylmethane diisocyanates (poly-MDI), xylylene diisocyanate (MXDI) and Tetramethylxylylene diisocyanate (TMXDI).

Suitable aliphatic diisocyanates for use as diisocyanate B) include linear and / or branched alkylene radicals preferably having 3 to 16 carbon atoms, more preferably 4 to 12 carbon atoms. Suitable cycloaliphatic or (cyclo) aliphatic diisocyanates include a cycloalkylene radical preferably having 4 to 18 carbon atoms, more preferably 6 to 15 Carbon atoms. Examples of suitable disocyanates include cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, heptane diisocyanate, octane diisocyanate, nonane diisocyanate such as 4-isocyanatomethyl-1,8-octane diisocyanate (TIN), decane and triisocyanate, undecanedi and triisocyanate, dodecanedi and triisocyanates. Also suitable are 4-methylcyclohexane-1,3-diisocyanate, 2-butyl-2-ethylpentamethylene diisocyanate, 3 (4) isocyanatomethyl-1-methylcyclohexyl isocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 2,4'-methylenebis (cyclohexyl ) diisocyanate and / or 1,4-diisocyanato-4-methyl-pentane.

Preferred diisocyanates B) are isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 2,2'-dicyclohexylmethane diisocyanate (2,2'-H12MDI), 2,4'-dicyclohexylmethane diisocyanate (2,4'-H12MDI), 4,4'- Dicyclohexylmethane diisocyanate (4,4'-H12MDI), 2-methylpentane diisocyanate (MPDI), 2,2,4-trimethylhexamethylene diisocyanate (2,2,4-TMDI), 2,4,4-trimethylhexamethylene diisocyanate (2,4,4-TMDI) , Norbornane diisocyanate (NBDI), methylene diphenyl diisocyanate (MDI), toluidine diisocyanate (TDI), tetramethylxylylene diisocyanate (TMXDI), individually or mixtures thereof.

In a particularly preferred embodiment, the diisocyanate B) is IPDI and / or 4,4'-H12MDI and / or HDI and / or a mixture of 2,2,4-TMDI and 2,4,4-TMDI.

As diols C) and polyols C) z. Ethylene glycol, 1,2-, 1,3-propanediol, diethylene, dipropylene, triethylene, tetraethylene glycol, 1,2-, 1,4-butanediol, 1,3-butylethylpropanediol, 1,3-methylpropanediol, 1 , 5-pentanediol, bis (1,4-hydroxymethyl) cyclohexane (cyclohexanedimethanol), glycerol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, bisphenol A, B, C, F, norbornylene glycol, 1,4-benzyldimethanol, ethanol , 2,4-dimethyl-2-ethylhexane-1,3-diol, 1,4- and 2,3-butylene glycol, di-β-hydroxyethylbutanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8- Octanediol, decanediol, dodecanediol, neopentyl glycol, cyclohexanediol, 3 (4), 8 (9) -bis (hydroxymethyl) -tricyclo [5.2.1.0 ^2,6 ] decane (dicidol), 2,2-bis (4-hydroxycyclohexyl) propane, 2,2-bis [4- (β-hydroxyethoxy) -phenyl] propane, 2-methyl-1,3-propanediol, 2-methylpentanediol-1,5, 2,2,4 (2,4,4 ) -Trimethylhexanediol-1,6, hexanetriol-1,2,6, butanetriol-1,2,4,2,2-dimethylpropanediol- (1,3), heptanediol- (1,7), octa-decene-9, 10-diol (1,12), thiodiglycol, octadecanediol (1,18), 2,4-dimethyl-2- propylheptanediol- (1,3), tris (.beta.-hydroxyethyl) isocyanurate, mannitol, sorbitol, polypropylene glycols, polybutylene glycols, xylylene glycol or hydroxypivalic acid neopentyl glycol esters, used alone or in mixtures.

Particularly preferred diols C) and polyols C) are ethylene glycol, triethylene glycol, 1,4-butanediol, 1,2-propanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, decanediol, 1,12-dodecanediol, 2,2,4-trimethylhexanediol-1,6, 2,4,4-trimethylhexanediol-1,6, 2,2-dimethyl-1,3-butanediol, 2-methyl-pentanediol-2,4, 3-methyl- 2,4-pentanediol, 2,2,4-trimethylpentanediol-1,3,2-ethylhexanediol-1,3,2,2-dimethylhexanediol-1,3,3-methylpentanediol-1,5, 2-methyl- pentanediol-1,5, trimethylolpropane, 2,2-dimethylpropanediol-1,3 (neopentyl glycol), hydroxypivalic acid neopentyl glycol ester and cis / trans-1,4-cyclohexanediol, alone or in mixtures.

Very particularly preferred diols C) and polyols C) are 1,5-pentanediol, 1,6-hexanediol, 1,12-dodecanediol, 2,2,4-trimethylhexanediol-1,6, 2,4,4-trimethylhexanediol-1 , 6,2,2-Dimethyl-1,3-butanediol, 2-methylpentanediol-2,4, 3-methyl-pentanediol-2,4, 2,2,4-trimethyl-pentanediol-1,3,2 Ethylhexanediol-1,3,2,2-dimethylhexanediol-1,3, 3-methylpentanediol-1,5, 2-methylpentanediol-1,5, 2,2-dimethylpropanediol-1,3 (neopentyl glycol) and cis / trans-1,4-cyclohexanediol, alone or in mixtures.

As component C) preferably hydroxyl-containing polyesters, polyethers, polyacrylates, polycarbonates and polyurethanes having an OH number of 20 to 500 mg KOH / g and an average molecular weight of 250 to 6000 g / mol are used. Hydroxyl-containing polyesters or polyacrylates having an OH number of 50 to 250 mg KOH / g and an average molecular weight of 500 to 6000 g / mol are particularly preferably used in the context of the present invention. The hydroxyl number (OH number, OH) is determined according to DIN 53240-2. In this method, the sample is reacted with acetic anhydride in the presence of 4-dimethylaminopyridine as a catalyst to acetylate the hydroxyl groups. One molecule of acetic acid is formed per hydroxyl group, while the subsequent hydrolysis of the excess acetic anhydride yields two molecules of acetic acid. The consumption of acetic acid is determined titrimetrically from the difference between the main value and a blank value to be carried out in parallel. The molecular weight is determined by gel permeation chromatography (GPC). The characterization of the samples is carried out in tetrahydrofuran as eluent according to DIN 55672-1.

Hydroxyl-containing (meth) acrylic copolymer used as component C) can be resins having a monomer composition, as described, for example, in US Pat. In WO 93/15849 8, line 25 to page 10, line 5, wherein the acid value of the (meth) acrylic copolymer to be set by proportionate use of (meth) acrylic acid as the monomer should be 0 to 30, preferably 0 to 30 15 mg KOH / g The number average molecular weight (determined by gel permeation chromatography against a polystyrene standard) of the (meth) acrylic copolymer is preferably 2000 to 20 000 g / mol, the glass transition temperature is preferably - 40 ° C to + 60 ° C and by Proportional use of hydroxyalkyl (meth) acrylates to be adjusted hydroxyl content of the invention to The (meth) acrylic copolymer used is preferably from 20 to 500 mg KOH / g, more preferably from 50 to 250 mg KOH / g.

According to the invention as component C) suitable polyester polyols are resins having a monomer composition of di- and polycarboxylic acids and di- and polyols, as described in the WO 93/15849 are described. As polyester polyols and polyaddition products of caprolactone to low molecular weight di- and triols, as z. B. under the name CAPA® (Perstorp) are available used. The mathematically determined number average molecular weight is preferably 500 to 5000 g / mol, more preferably 800 to 3000 g / mol, the average functionality is preferably 2.0 to 4.0, preferably 2.0 to 3.5.

In principle, those urethane- and ester-group-containing polyols to be used according to the invention as component C) also include those used in EP 140 186 are described. Preference is given to urethane- and ester-containing polyols, for the preparation of which HDI, IPDI, trimethylhexamethylene diisocyanate (TMDI) or dicyclohexylmethane diisocyanate (H12MDI) are used. The number average molecular weight is preferably 500-5000 g / mol, the average functionality is in particular in the range from 2.0 to 3.5.

Suitable components C) are diols and polyols which contain further functional groups. These are the linear or branched hydroxyl-containing polyesters, polycarbonates, polycaprolactones, polyethers, polythioethers, polyesteramides, polyurethanes or polyacetals known per se. They preferably have a number average molecular weight of 134 to 3,500 g / mol. Preference is given to linear hydroxyl-containing polyester-polyesterpolyols-or mixtures of such polyesters. They are z. Example by reacting diols with minor amounts of dicarboxylic acids, corresponding dicarboxylic anhydrides, corresponding dicarboxylic acid esters of lower alcohols, lactones or hydroxycarboxylic acids produced.

Diols which are suitable for the preparation of the polyesterpolyols are, in addition to the abovementioned diols, also 2-methylpropanediol, 2,2-dimethylpropanediol, diethylene glycol, dodecanediol-1,12, 1,4-cyclohexanedimethanol and 1,2- and 1,4-cyclohexanediol.

Suitable dicarboxylic acids or derivatives for the preparation of the polyester polyols may be aliphatic, cycloaliphatic, aromatic and / or heteroaromatic nature and optionally, for. B. by halogen atoms, substituted and / or unsaturated.

Preferred dicarboxylic acids or derivatives include succinic, adipic, corkic, azelaic and sebacic acids, 2,2,4 (2,4,4) -trimethyladipic acid, phthalic acid, phthalic anhydride, Isophthalic acid, terephthalic acid, terephthalic acid dimethyl ester, tetrahydrophthalic acid, maleic acid, maleic anhydride and dimer fatty acids.

Suitable polyester polyols are also those which can be prepared in a known manner by ring opening from lactones, such as epsilon-caprolactone, and simple diols as starter molecules.

The diols and dicarboxylic acids or derivatives thereof used for the preparation of the polyesterpolyols can be used in any desired mixtures.

Of course, mixtures of components C) described above can also be used.

The ratio of the NCO groups of the reaction product I. to the OH groups of the diol and / or polyol II. C) varies from 1.0: 1.5 to 1.0: 0.6, preferably 1.15: 1 to 0.85: 1, more preferably 1: 1.

The preparation of the alkoxysilane-functionalized and allophanate-functionalized binder component a) according to the invention is carried out in two steps. In step I., the monourethane A) is reacted with the diisocyanate B), resulting in the reaction product I. This is followed by step II. In which the reaction product I. is reacted to form urethane with diols and / or polyols.

In general, step I. and II. Solvent-free or using non-protic solvents, the reaction can be carried out batchwise or continuously. The reactions of step I. and II. Are carried out in suitable aggregates, e.g. Stirred tank, extruder, static mixers, kneading chambers. The reactions of step I. and II can be carried out at room temperature, that is to say at temperatures in the range from 15 to 40.degree. C., in particular in the range from 15 to 25.degree. However, preference is given to using higher temperatures in the range from 80 to 220.degree. C., in particular in the range from 80 to 120.degree. The reactions of step I. and II. Are carried out in the absence of water. The reactions of step I. and II. Are preferably carried out solvent-free.

To accelerate the reactions of step I. and II. Advantageously in the urethane chemistry known catalysts K), for example organometallic compounds, such as tin or zinc-containing compounds, salts, such as Zn (II) chloride and / or bases can be used. For example, Sn, Bi, Zn and other metal carboxylates such as z, B are suitable. Dibutyltin dilaurate, tin octoate, zinc (II) ethylhexanoate, bismuth neodecanoate, tertiary amines such as 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU ), 1,5-diazabicyclo [4.3.0] non-5-ene (DBN), triethylamine, amidines and guanidines, and quaternary ammonium salts, preferably tetralkylammonium salts and / or quaternary phosphonium salts.

As catalysts K) also Metallacetylacetonate come into question. Examples of these are zinc acetylacetonate, lithium acetylacetonate, iron acetylacetonate and tin acetylacetonate, alone or in mixtures. Also suitable as catalysts are quaternary ammonium acetylacetonates or quaternary phosphonium acetylacetonates.

Zinc acetylacetonate or zinc ethylhexanoate are preferably used for the reaction of step I.

The coating composition according to the invention contains as component b) at least one binder component. In principle, all types of binders known to the person skilled in the art, for example thermoplastic, ie non-crosslinkable, binders which usually have an average molecular weight> 10000 g / mol are suitable as binders. However, preference is given to binders which react via reactive functional groups with acidic hydrogen atoms z. As hydroxyl or primary or secondary amine groups have. Suitable binders of the type mentioned have, for example, at least one, but preferably two or more hydroxyl groups. Further suitable functional groups of the binder are, for example, alkoxysilane functionalities.

As binder component b) with functional groups it is preferred to use hydroxyl-containing polyesters, polyethers, polyacrylates, polycarbonates and polyurethanes having an OH number of 20 to 500 mg KOH / g and an average molecular weight of 250 to 6000 g / mol. Hydroxyl-containing polyesters or polyacrylates having an OH number of 50 to 250 mg KOH / g and an average molecular weight of 500 to 6000 g / mol are particularly preferably used as binder components in the context of the present invention. The hydroxyl number (OH number, OH) is determined according to DIN 53240-2. In this method, the sample is reacted with acetic anhydride in the presence of 4-dimethylaminopyridine as a catalyst to acetylate the hydroxyl groups. One molecule of acetic acid is formed per hydroxyl group, while the subsequent hydrolysis of the excess acetic anhydride yields two molecules of acetic acid. The consumption of acetic acid is determined titrimetrically from the difference between the main value and a blank value to be carried out in parallel. The molecular weight is determined by gel permeation chromatography (GPC). The characterization of the samples is carried out in tetrahydrofuran as eluent according to DIN 55672-1.

As a binder component b) used hydroxyl-containing (meth) acrylic copolymer can resins having a monomer composition, as z. In WO 93/15849 (P. 8, line 25 to page 10, line 5, are used. In this case, the acid number of the (meth) acrylic copolymer to be set by proportionate use of (meth) acrylic acid as monomer should be 0 to 30, preferably 0 to 15 mg KOH / g. The number average molecular weight (determined by gel permeation chromatography against a polystyrene standard) of the (meth) acrylic copolymer is preferably 2000 to 20 000 g / mol, the glass transition temperature is preferably - 40 ° C to + 60 ° C. The hydroxyl content of the (meth) acrylic copolymers to be used according to the invention to be adjusted by proportionate use of hydroxyalkyl (meth) acrylates is preferably 20 to 500 mg KOH / g, more preferably 50 to 250 mg KOH / g.

According to the invention as binder component b) suitable polyester polyols are resins with a monomer composition of di- and polycarboxylic acids and di- and polyols, as described in the WO 93/15849 are described. As polyester polyols and polyaddition products of caprolactone to low molecular weight di- and triols, as z. B. under the name CAPA® (Perstorp) are available used. The mathematically determined number average molecular weight is preferably 500 to 5000 g / mol, more preferably 800 to 3000 g / mol, the average functionality is preferably 2.0 to 4.0, preferably 2.0 to 3.5.

In principle, those urethane- and ester-group-containing polyols to be used according to the invention as binder component b) also include those used in EP 140 186 are described. Preference is given to urethane- and ester-containing polyols, for the preparation of which HDI, IPDI, trimethylhexamethylene diisocyanate (TMDI) or dicyclohexylmethane diisocyanate (H12MDI) are used. The number average molecular weight is preferably 500-5000 g / mol, the average functionality is in particular in the range from 2.0 to 3.5.

Trialkoxysilane-functional binders are also suitable for use as component b). Such resins can be obtained by copolymerization of acrylate or methacrylate monomers with acrylic or methacrylic-functional alkyl trialkoxysilane derivatives (eg, Dynasylan MEMO from Evonik Industries AG), such as in US Pat WO 92/11328 described. An alternative synthetic route consists of the derivatization of hydroxyl-containing polyethers, polyesters, polycarbonate diols or polyacrylates with isocyanatopropyltrialkoxysilane, as described, for example, in US Pat WO2008 / 131715 in Examples 3 and 4 is described. Amino-containing binders are also suitable, for example, aminopropyltrimethoxysilane (eg Dynasylan AMMO from Evonik Industries AG), aminopropyltriethoxysilane, aminomethyltrimethoxysilane or aminomethyltriethyoxysilane.

Of course, it is also possible to use mixtures of the binder components b) described above.

Particularly preferred binder components b) are hydroxyl-containing polyesters and polyacrylates, alone or in mixtures.

The proportion of binder component b) in the binder according to the invention is preferably 1 to 90 percent by weight, based on the sum of components a), b) and optionally c) and d), preferably 20 to 60 percent by weight.

Component c)

The polyisocyanates c) used according to the invention can consist of any desired aromatic, aliphatic, cycloaliphatic and / or (cyclo) aliphatic polyisocyanates.

As aromatic polyisocyanates c), in principle all known aromatic compounds are suitable. Particularly suitable are 1,3- and 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, 2,6-tolylene diisocyanate (2,6-TDI), 2,4-tolylene diisocyanate (2,4-TDI), 2, 4'-diphenylmethane diisocyanate (2,4'-MDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), the mixtures of monomeric diphenylmethane diisocyanates (MDI) and oligomeric diphenylmethane diisocyanates (poly-MDI), xylylene diisocyanate (MXDI) and Tetramethylxylylene diisocyanate (TMXDI).

The aliphatic or cycloaliphatic polyisocyanate c) used as crosslinking component c) comprises at least one aliphatic and / or cycloaliphatic polyisocyanate having an NCO functionality of at least 2, preferably 2 to 6, more preferably 2.8 to 6, most preferably 2 to 4. Unter The term "NCO functionality" as used herein means the number of reactive NCO substituents on average having the corresponding molecule, preferably crosslinker component c).

The polyisocyanate c) used according to the invention as component c) according to the invention can be any desired aliphatic, cycloaliphatic and / or (cyclo) aliphatic diisocyanate. Under (cyclo) aliphatic diisocyanates, the skilled worker understands at the same time cyclic and aliphatic bound NCO groups, as z. B. isophorone diisocyanate is the case. In contrast, is meant by cycloaliphatic diisocyanates those which have only directly attached to the cycloaliphatic ring NCO groups, for. Eg H12MDI.

Aliphatic polyisocyanates suitable for use as component c) of the present invention include a linear or branched alkylene group having preferably 3 to 16 carbon atoms, more preferably 4 to 12 carbon atoms. Suitable cycloaliphatic or (cyclo) aliphatic polyisocyanates c) comprise a cycloalkylene radical having preferably 4 to 18 carbon atoms, more preferably 6 to 15 carbon atoms. Examples of suitable di- or polyisocyanates include cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, heptane diisocyanate, octane diisocyanate, nonane diisocyanate, nonane triisocyanate such as 4-isocyanatomethyl-1,8-octane diisocyanate (TIN), decane and triisocyanate. Undekandi- and triisocyanate, dodecandi- and triisocyanates. Also suitable are 4-methylcyclohexane-1,3-diisocyanate, 2-butyl-2-ethylpentamethylene diisocyanate, 3 (4) isocyanatomethyl-1-methylcyclohexyl isocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 2,4'-methylenebis (cyclohexyl ) diisocyanate and / or 1,4-diisocyanato-4-methyl-pentane.

The polyisocyanate used as component c) according to the invention is preferably selected from isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 2,2'-di-cyclohexylmethane diisocyanate (2,2'-H12MDI), 2,4'-dicyclohexylmethane diisocyanate (2,4'-H12MDI ), 4,4'-dicyclohexylmethane diisocyanate (4,4'-H12MDI), 2-methylpentane diisocyanate (MPDI), pentane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate (2,2,4-TMDI), 2,4,4-trimethylhexamethylene diisocyanate (2,4,4 TMDI), norbornane diisocyanate (NBDI), methylene diphenyl diisocyanate (MDI), toluidine diisocyanate (TDI), tetramethylxylylene diisocyanate (TMXDI), xylylene diisocyanate (MXDI), individually or mixtures thereof.

The polyisocyanate used as component c) according to the invention is particularly preferably selected from the group consisting of isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), diisocyanato-dicyclohexylmethane (H12MDI), 2-methylpentane diisocyanate (MPDI), 2,2,4-trimethylhexamethylene diisocyanate / 2 , 4,4-trimethylhexamethylene diisocyanate (TMDI), norbornane diisocyanate (NBDI). Particularly preferred are IPDI, HDI, TMDI and / or H12MDI, with IPDI, H12MDI and / or HDI being the most preferred polyisocyanates.

It is also preferred as component c) according to the invention polyisocyanates which are obtained from the diisocyanates mentioned or mixtures thereof by linking by means of urethane, allophanate, urea, biuret, uretdione, amide, isocyanurate, carbodiimide, uretonimine , Oxadiazinetrione or iminooxadiazinedione structures. Such polyisocyanates are available commercially.
Particularly preferred components c) according to the invention are isocyanurates, in particular isocyanurates of IPDI and / or HDI, for example VESTANAT HT 2500 L and VESTANAT T 1890. Such polyisocyanates may optionally be reacted with di- or polyfunctional, H-acidic components, such as. As di- or polyols and / or di- or polyamines, additionally chain-extended or branched.

As components c) according to the invention it is particularly preferable to use isocyanurates which are freed from residual monomers by distillative separation, so that the content of polyisocyanate residual monomer is <0.5% by weight.

In the context of the present invention, it is possible to use any desired mixtures of the diisocyanates and / or polyisocyanates described above.

The component c), if present, in the coating composition of the invention to 5 to 50 weight percent, preferably 15 to 40 weight percent, based on the sum of components a), b), optionally c) and d) included.

As catalyst d) is in a preferred embodiment in an amount of 0.1 to 5 weight percent, preferably 0.2 to 3 weight percent, based on the sum of components a), b), optionally c) and d), in Contain the coating agent of the invention.

As catalysts d) organic carboxylic acids can be used. Examples of suitable carboxylic acids are in particular salicylic acid, benzoic acid, citric acid, phthalic acid, terephthalic acid, isophthalic acid, dodecanoic acid, 1.12-dodecanedioic acid and / or ascorbic acid. Salicylic acid, citric acid or benzoic acid are preferably used, but mixtures of said carboxylic acids can be used.

• Tetramethylammoniumformiat, Tetramethylammoniumacetat, Tetramethylammoniumpropionat,
• Tetramethylammoniumbutyrat, Tetramethylammonium-benzoat, Tetraethylammoniumformiat,
• Tetraethylammoniumacetat, Tetraethylammoniumpropionat, Tetraethylammoniumbutyrat,
• Tetraethylammoniumbenzoat, Tetrapropylammoniumformiat, Tetrapropylammoniumacetat,
• Tetrapropylammoniumpropionat, Tetrapropylammoniumbutyrat, Tetrapropylammoniumbenzoat,
• Tetrabutylammoniumformiat, Tetrabutylammoniumacetat, Tetrabutylammoniumpropionat,
• Tetrabutylammoniumbutyrat und Tetrabutylammoniumbenzoat und Tetrabutylphosphoniumacetat,
• Tetrabutylphosphoniumformiat und Ethyltriphenylphosphoniumacetat,
• Tetrabutylphosphoniumbenzotriazolat, Tetraphenylphosphoniumphenolat und Trihexyltetradecylphosphoniumdecanoat, Methyltributylammoniumhydroxid,
• Methyltriethylammoniumhydroxid, Tetramethylammoniumhydroxid, Tetraethylammoniumhydroxid,
• Tetrapropylammoniumhydroxid, Tetrabutylammoniumhydroxid, Tetrapentylammoniumhydroxid,
• Tetrahexylammoniumhydroxid, Tetraoctylammoniumhydroxid, Tetradecylammoniumhydroxid,
• Tetradecyltrihexylammoniumhydroxid, Tetraoctadecylammoniumhydroxid,
• Benzyltrimethylammoniumhydroxid, Benzyltriethylammoniumhydroxid, Trimethylphenylammoniumhydroxid, Triethylmethylammoniumhydroxid, Trimethylvinylammoniumhydroxid, Methyltributylammoniummethanolat,
• Methyltriethylammoniummethanolat, Tetramethylammoniummethanolat,
• Tetraethylammoniummethanolat, Tetrapropylammoniummethanolat,
• Tetrabutylammoniummethanolat, Tetrapentylammoniummethanolat,
• Tetrahexylammoniummethanolat, Tetraoctylammoniummethanolat,
• Tetradecylammoniummethanolat, Tetradecyltrihexylammoniummethanolat,
• Tetraoctadecylammoniummethanolat, Benzyltrimethylammoniummethanolat,
• Benzyltriethylammoniummethanolat, Trimethylphenylammoniummethanolat,
• Triethylmethylammoniummethanolat, Trimethylvinylammoniummethanolat,
• Methyltributylammoniumethanolat, Methyltriethylammoniumethanolat,
• Tetramethylammoniumethanolat, Tetraethylammoniumethanolat, Tetrapropylammoniumethanolat,
• Tetrabutylammoniumethanolat, Tetrapentylammoniumethanolat, Tetrahexylammoniumethanolat,
• Tetraoctylammoniummethanolat, Tetradecylammoniumethanolat,
• Tetradecyltrihexylammoniumethanolat, Tetraoctadecylammoniumethanolat,
• Benzyltrimethylammoniumethanolat, Benzyltriethylammoniumethanolat, Tri methylphenylammoniumethanolat, Triethylmethylammoniumethanolat, Tri methylvinylammoniumethanolat, Methyltributylammoniumbenzylat,
• Methyltriethylammoniumbenzylat, Tetramethylammoniumbenzylat, Tetraethylammoniumbenzylat,
• Tetrapropylammoniumbenzylat, Tetrabutylammoniumbenzylat, Tetrapentylammoniumbenzylat,
• Tetrahexylammoniumbenzylat, Tetraoctylammoniumbenzylat, Tetradecylammoniumbenzylat,
• Tetradecyltrihexylammoniumbenzylat, Tetraoctadecylammoniumbenzylat,
• Benzyltrimethylammoniumbenzylat, Benzyltriethylammoniumbenzylat, Trimethylphenylammoniumbenzylat, Triethylmethylammoniumbenzylat, Trimethylvinylammoniumbenzylat, Tetramethylammoniumfluorid, Tetraethylammoniumfluorid,
• Tetrabutylammoniumfluorid, Tetraoctylammoniumfluorid, Benzyltrimethylammoniumfluorid,
• Tetrabutylphosphoniumhydroxid, Tetrabutylphosphoniumfluorid, Tetrabutylammoniumchlorid,
• Tetrabutylammoniumbromid, Tetrabutylammoniumiodid, Tetraethylammoniumchlorid,
• Tetraethylammoniumbromid, Tetraethylammoniumiodid, Tetramethylammoniumchlorid,
• Tetramethylammoniumbromid, Tetramethylammoniumiodid, Benzyltrimethylammoniumchlorid,
• Benzyltriethylammoniumchlorid, Benzyltripropylammoniumchlorid, Benzyltributylammoniumchlorid,
• Methyltributylammoniumchlorid, Methyltripropylammoniumchlorid, Methyltriethylammoniumchlorid,
• Methyltriphenylammoniumchlorid, Phenyltrimethylammoniumchlorid,
• Benzyltrimethylammoniumbromid, Benzyltriethylammoniumbromid,
• Benzyltripropylammoniumbromid, Benzyltributylammoniumbromid, Methyltributylammoniumbromid,
• Methyltripropylammoniumbromid, Methyltriethylammoniumbromid,
• Methyltriphenylammoniumbromid, Phenyltrimethylammoniumbromid,
• Benzyltrimethylammoniumiodid, Benzyltriethylammoniumiodid, Benzyltripropylammoniumiodid,
• Benzyltributylammoniumiodid, Methyltributylammoniumiodid, Methyltripropylammoniumiodid,
• Methyltriethylammoniumiodid, Methyltriphenylammoniumiodid und Phenyltrimethylammoniumiodid,
• Methyltributylammoniumhydroxid, Methyltriethylammoniumhydroxid,
• Tetramethylammoniumhydroxid, Tetraethylammoniumhydroxid, Tetrapropylammoniumhydroxid,
• Tetrabutylammoniumhydroxid, Tetrapentylammoniumhydroxid, Tetrahexylammoniumhydroxid,
• Tetraoctylammoniumhydroxid, Tetradecylammoniumhydroxid,
• Tetradecyltrihexylammoniumhydroxid, Tetraoctadecylammoniumhydroxid,
• Benzyltrimethylammoniumhydroxid, Benzyltriethylammoniumhydroxid,
• Trimethylphenylammoniumhydroxid, Triethylmethylammoniumhydroxid,
• Trimethylvinylammoniumhydroxid, Tetramethylammoniumfluorid, Tetraethylammoniumfluorid,
• Tetrabutylammoniumfluorid, Tetraoctylammoniumfluorid und Benzyltrimethylammoniumfluorid.

Also used as catalyst d) are quaternary ammonium salts, alone or in mixtures, preferably tetralkylammonium salts and / or quaternary phosphonium salts with halogens, hydroxides, alcoholates or organic or inorganic acid anions as counterion. Examples are:

• Tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate,
• Tetramethylammonium butyrate, tetramethylammonium benzoate, tetraethylammonium formate,
• Tetraethylammonium acetate, tetraethylammonium propionate, tetraethylammonium butyrate,
• Tetraethylammonium benzoate, tetrapropylammonium formate, tetrapropylammonium acetate,
• Tetrapropylammonium propionate, tetrapropylammonium butyrate, tetrapropylammonium benzoate,
• Tetrabutylammonium formate, tetrabutylammonium acetate, tetrabutylammonium propionate,
• Tetrabutylammonium butyrate and tetrabutylammonium benzoate and tetrabutylphosphonium acetate,
• Tetrabutylphosphonium formate and ethyltriphenylphosphonium acetate,
• Tetrabutylphosphonium benzotriazolate, tetraphenylphosphonium phenolate and trihexyltetradecylphosphonium decanoate, methyltributylammonium hydroxide,
• Methyltriethylammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide,
• Tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide,
• Tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, tetradecylammonium hydroxide,
• Tetradecyltrihexylammonium hydroxide, tetraoctadecylammonium hydroxide,
• Benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, trimethylvinylammonium hydroxide, methyltributylammonium methoxide,
• Methyltriethylammonium methoxide, tetramethylammonium methoxide,
• Tetraethylammonium methoxide, tetrapropylammonium methoxide,
• Tetrabutylammonium methoxide, tetrapentylammonium methoxide,
• Tetrahexylammonium methoxide, tetraoctylammonium methoxide,
• Tetradecylammonium methoxide, tetradecyltrihexylammonium methoxide,
• Tetraoctadecylammonium methoxide, benzyltrimethylammonium methoxide,
• Benzyltriethylammonium methoxide, trimethylphenylammonium methoxide,
• Triethylmethylammonium methoxide, trimethylvinylammonium methoxide,
• Methyltributylammoniumethanolate, methyltriethylammoniumethanolate,
• Tetramethylammoniumethanolate, tetraethylammoniumethanolate, tetrapropylammoniumethanolate,
• Tetrabutylammoniumethanolate, tetrapentylammoniumethanolate, tetrahexylammoniumethanolate,
• Tetraoctylammonium methoxide, tetradecylammonium ethanolate,
• Tetradecyltrihexylammoniumethanolate, tetraoctadecylammoniumethanolate,
• Benzyltrimethylammoniumethanolat, Benzyltriethylammoniumethanolat, Tri methylphenylammoniumethanolat, Triethylmethylammoniumethanolat, Tri methylvinylammoniumethanolat, Methyltributylammoniumbenzylat,
• Methyltriethylammoniumbenzylate, tetramethylammoniumbenzylate, tetraethylammoniumbenzylate,
• Tetrapropylammonium benzylate, tetrabutylammonium benzylate, tetrapentylammoniumbenzylate,
• Tetrahexylammonium benzylate, tetraoctylammoniumbenzylate, tetradecylammoniumbenzylate,
• Tetradecyltrihexylammoniumbenzylate, tetraoctadecylammoniumbenzylate,
• Benzyltrimethylammonium benzylate, benzyltriethylammonium benzylate, trimethylphenylammonium benzylate, triethylmethylammonium benzylate, trimethylvinylammonium benzylate, tetramethylammonium fluoride, tetraethylammonium fluoride,
• Tetrabutylammonium fluoride, tetraoctylammonium fluoride, benzyltrimethylammonium fluoride,
• Tetrabutylphosphonium hydroxide, tetrabutylphosphonium fluoride, tetrabutylammonium chloride,
• Tetrabutylammonium bromide, tetrabutylammonium iodide, tetraethylammonium chloride,
• Tetraethylammonium bromide, tetraethylammonium iodide, tetramethylammonium chloride,
• Tetramethylammonium bromide, tetramethylammonium iodide, benzyltrimethylammonium chloride,
• Benzyltriethylammonium chloride, benzyltripropylammonium chloride, benzyltributylammonium chloride,
• Methyltributylammonium chloride, methyltripropylammonium chloride, methyltriethylammonium chloride,
• Methyltriphenylammonium chloride, phenyltrimethylammonium chloride,
• Benzyltrimethylammonium bromide, benzyltriethylammonium bromide,
• Benzyltripropylammonium bromide, benzyltributylammonium bromide, methyltributylammonium bromide,
• Methyltripropylammonium bromide, methyltriethylammonium bromide,
• Methyltriphenylammonium bromide, phenyltrimethylammonium bromide,
• Benzyltrimethylammonium iodide, benzyltriethylammonium iodide, benzyltripropylammonium iodide,
• Benzyltributylammonium iodide, methyltributylammonium iodide, methyltripropylammonium iodide,
• Methyltriethylammonium iodide, methyltriphenylammonium iodide and phenyltrimethylammonium iodide,
• Methyltributylammonium hydroxide, methyltriethylammonium hydroxide,
• Tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide,
• Tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide,
• Tetraoctylammonium hydroxide, tetradecylammonium hydroxide,
• Tetradecyltrihexylammonium hydroxide, tetraoctadecylammonium hydroxide,
• Benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide,
• Trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide,
• Trimethylvinylammonium hydroxide, tetramethylammonium fluoride, tetraethylammonium fluoride,
• Tetrabutylammonium fluoride, tetraoctylammonium fluoride and benzyltrimethylammonium fluoride.

These catalysts may be added alone or in mixtures. Preference is given to using tetraethylammonium benzoate and tetrabutylammonium hydroxide.

As catalyst d) it is also possible to use metal complexes with chelate ligands. The chelating ligands are organic compounds having at least two functional groups that can coordinate to metal atoms or ions. For example, the aluminum and zirconium chelate complexes, as described for example in US Pat 4,772,672 A , are used as catalyst. Preferred metal chelates are chelates based on zinc, lithium, tin, aluminum, zirconium, titanium and / or boron, such as, for example, aluminum ethylacetoacetate, zirconium ethylacetoacetate, zinc acetylacetonate, lithium acetylacetonate and tin acetylacetonate, alone or in mixtures. Zinc acetylacetonate is preferably used.

Other suitable catalysts d) are quaternary ammonium acetylacetonates or quaternary phosphonium acetylacetonates.
Examples of such catalysts are Tetramethylammoniumacetylacetonat, Tetraethylammoniumacetylacetonat, Tetrapropylammoniumacetylacetonat, Tetrabutylammoniumacetylacetonat, Benzyltrimethylammoniumacetylacetonat, Benzyltriethylammoniumacetylacetonat, Tetramethylphosphoniumacetylacetonat, Tetraethylphosphoniumacetylacetonat, Tetrapropylphosphoniumacetylacetonat, Tetrabutylphosphoniumacetylacetonat, Benzyltrimethylphosphoniumacetylacetonat, Benzyltriethylphosphoniumacetylacetonat. Particular preference is given to using tetraethylammonium acetylacetonate and tetrabutylammonium acetylacetonate. Of course, mixtures of such catalysts can be used.

As catalyst d) aluminum, zirconium, titanium and / or boron alcoholates and / or esters thereof are also suitable.

Also suitable as catalysts are basic substances such as guanidines and amidines and tertiary amines. Examples of these are tetramethylguanidine, diazabicyloundecene (DBU), diazabicyclononene (DBN), and diazabicyclooctane (DABCO).

As catalyst d) catalysts can be used for catalysis of the urethane reaction, which have been proven in the field of PUR technology, z. As organic Sn (IV) - Sn (II), Zn, Bi compounds, or organometallic catalysts, such as. As dibutyltin dilaurate, tin octoate, zinc ethylhexanoate, bismuth neodecanoate, or tertiary amines, such as. For example, 1,4-diazabicyclo [2.2.2.] Octane. However, such catalysts for urethane reactions are used according to the invention only in blends with other catalysts of the invention. Zinc ethylhexanoate is preferably used.

As catalyst d) it is also possible to use a phosphorus-containing, preferably phosphorus- and nitrogen-containing catalyst. It is also possible to use mixtures of two or more different catalysts. Examples of suitable phosphorus-containing catalysts are substituted phosphonic diesters and diphosphonic diesters, preferably from the group consisting of acyclic phosphonic diesters, cyclic phosphonic diesters, acyclic diiphosphonic diesters and cyclic diphosphonic diesters. Such catalysts are for example in the DE-A 102005045228 described.

As catalyst d) it is also possible to use an amine-blocked phosphoric acid ester and particularly preferably amine-blocked phosphoric acid ethylhexyl ester and amine-blocked phosphoric acid phenyl ester. Examples of amines with which the phosphoric acid esters are blocked are, in particular, tertiary amines, for example triethylamine. Particularly preferred for blocking the phosphoric acid esters tertiary amines are used, which have a good activity of the catalyst at curing temperatures of 100 to 160 ° C. Certain amine-blocked phosphoric acid catalysts are also commercially available (eg, Nacure grades from King Industries). For example, the Nacure 4167 from King Industries is particularly suitable as a catalyst based on an amine-blocked phosphoric acid partial ester.

As catalyst d) it is also possible to use organic sulfonic acids in unblocked or blocked form. As sulfonic acid, basically any organic sulfonic acid is suitable, preferred are p-toluenesulfonic acid and dodecylbenzenesulfonic acid. For thermal, ie above 100 ° C crosslinking coating systems these sulfonic acids according to the invention can also be preferably used in amine-neutralized form. In accordance with the invention, it is also possible to use latent, nonionic sulfonic acid derivatives which release sulfonic acids only above 100 ° C., such as, for example, B. adducts of sulfonic acids to epoxide-containing components, as in DE-OS 23 56768 will be used. Salts of trifluoromethanesulfonic acid (triflates) are also suitable sulfonic acid-based catalysts.

Preference is given to using catalysts d) selected from tetraethylammonium benzoate, tetrabutylammonium hydroxide, tetraethylammonium acetylacetonate, tetrabutylammonium acetylacetonate, dibutyltin dilaurate, zinc acetylacetonate, zinc ethylhexanoate.

The catalyst d) in the coating composition n of the invention may consist solely of the abovementioned alternatives, but it is also possible to use any desired mixtures of the catalysts.

The coating composition of the invention may additionally be known in coating technology auxiliaries and / or additives e) such as stabilizers, light stabilizers, catalysts, additional crosslinkers, fillers, pigments, leveling agents or rheology aids, such as. As so-called. "Sag control agents", microgels or fumed silica or nanoparticles, such. In EP 1204701 B1 described, contained in typical concentrations. In addition, component e) may contain additional crosslinkers as known in coating chemistry, e.g. Example in the form of melamine, benzoguanamine resins, carbamatfunkionelle components or blocked polyisocyanates. If necessary, it is also possible to incorporate customary inorganic or organic color and / or effect pigments in coating technology in component e) of the coating compositions according to the invention.

In a preferred embodiment, the coating composition according to the invention is a pigment-free system, ie a clearcoat system. In this case, component e) may preferably be used in an amount of from 0.5 to 8% by weight, more preferably from 1 to 6% by weight, based on the sum of components a), b), optionally c) and d), in which Be contained coating compositions according to the invention.

In a further preferred embodiment, the coating composition according to the invention is a colored coating system. Pigments and fillers as component e) may in this case be present in an amount of from 10 to 200 percent by weight, based on the sum of components a), b), if appropriate c) and d), in the coating composition according to the invention.

Furthermore, the coating composition according to the invention may contain organic solvents as component f). Suitable solvents are, for. As ketones, alcohols, esters or aromatics.

The component f) is preferably present in amounts of 20 to 150 weight percent, more preferably 30 to 60 weight percent, based on the sum of the components a), b), optionally c) and d), in the coating composition according to the invention.

The coating compositions according to the invention are prepared by mixing the components described above. The mixing can be carried out by mixers known to those skilled in the art, for example batchwise in stirred tanks, dissolvers, bead mills, roller mills, etc., or also continuously using z. B. static mixers done.

The invention also provides the use of the alkoxysilane-functionalized allophanate-containing coating compositions in coating compositions and adhesive compositions and sealant compositions and metal coating compositions.

The invention also provides the use of the alkoxysilane-functionalized allophanate-containing coating compositions in coating compositions and paint compositions for metal, glass, plastic, wood, MDF (Middle Density Fiber Boards) or leather substrates or other heat-resistant substrates.

The invention also provides the use of the alkoxysilane-functionalized allophanate-containing coating compositions according to the invention in adhesive compositions for bonding metal, plastic, glass, wood, MDF or leather substrates or other heat-resistant substrates.

The invention also relates to metal coating compositions, in particular for automobile bodies, motorcycles and bicycles, building parts and household appliances, wood coating compositions, MDF coatings, glass coating compositions, leather coating compositions and plastic coating compositions.

The present invention is further illustrated by the following non-limiting examples to which further features, embodiments, aspects and advantages of the present invention may be derived.

Examples: Starting Materials:

• Vestanat® EP-UPMS: Trimethoxysilylpropylmethylcarbamate (Evonik Resource Efficiency GmbH),
• Vestanat® IPDI: isophorone diisocyanate (Evonik Resource Efficiency GmbH)
• Vestanat® TMDI: Mixture of 2,2,4-trimethylhexamethylene diisocyanate (2,2,4-TMDI) and 2,4,4-trimethylhexamethylene diisocyanate (Evonik Resource Efficiency GmbH)
• Vestanat® HT 2500/100: hexamethylene-1,6-diisocyanate, homopolymer (isocyanurate type) (Evonik Resource Efficiency GmbH)
• Vestanat® EP Cat 11 B: Tetraethylammonium benzoate in butanol (Evonik Resource Efficiency GmbH)
• Tegoglide® 410: slip and antiblocking additive based on a polyethersiloxane copolymer (Evonik Resource Efficiency GmbH)
• Vestanat® EP-M60: linear short-chain silane-functionalized crosslinker (Evonik Resource Efficiency GmbH)
• Vestanat® EP-M95: branched short-chain silane-functionalized crosslinker, (Evonik Resource Efficiency GmbH)
• Vestanat® EP-M120: linear long-chain silane-functionalized crosslinker, (Evonik Resource Efficiency GmbH)
• Setalux ^® 1760 VB-64: polyacrylate, Nuplex Resins BV
• Tinuvin ^® 292: hindered amine light stabilizers; BASF SE
• Tinuvin ^® 900: UV absorber; BASF SE

1. Preparation of a) Alkoxysilane and Allophanate Functionalized Urethane 1

36.9 g of Vestanat® EP-UPMS, 0.04 g of zinc (II) ethylhexanoate and 34.7 g of Vestanat® IPDI were placed in a three-necked flask with reflux condenser, covered with nitrogen and heated to 100 ° C. with stirring. After heating for 12 hours, an NCO content of 9.33% was obtained. The resulting allophanate was cooled, treated with 8.37 g of pentanediol and 0.01% DBTL and stirred at 60-65 ° C for 17 h until the NCO content of <0.1% was reached, after about 3 h for the purpose 20 g of butyl acetate were added. The alkoxysilane and allophanate functionalized urethane 1 thus obtained is a clear liquid having a viscosity of 3457 mPas (at 23 ° C).

Alkoxysilane and allophanate functionalized urethane 2

31.7 g of Vestanat® EP-UPMS, 0.04 g of zinc (II) ethylhexanoate and 29.8 g of Vestanat® IPDI were placed in a three-necked flask with reflux condenser, covered with nitrogen and heated to 100 ° C. with stirring. After heating for 6 hours, an NCO content of 9.12% was obtained. The resulting allophanate was cooled, treated with 13.5 g of dodecanediol and 0.01% DBTL and stirred at 60-65 ° C for several hours until the NCO content of <0.1% was reached, then was still in the heat for the purpose Viscosity reduction 20 g of 1-MOP-acetate were added. The alkoxysilane and allophanate functionalized urethane 2 thus obtained is a clear liquid having a viscosity of 1902 mPas (at 23 ° C).

2. Preparation of clearcoats from the alkoxysilane-functionalized and allophanate-functionalized coating compositions

For the formulation of the clearcoats of the invention and the comparative examples, the components of the compositions shown in Table 1 were mixed together immediately prior to processing.

The viscosity of the formulations, determined as the flow time in the DIN 4 cup at 23 ° C., was about 20 seconds. <b> Table 1: Composition of the clearcoat materials of the invention and comparative examples </ b> position I II III comparison IV comparison V comparison 1 Alkoxysilane and Allophanate Functionalized Urethane 1 28.78 2 Alkoxysilane and allophanate functionalized urethane 2 31,40 3 Comparative Example: Vestanat ^® EP-M95 26.79 4 Comparative Example: Vestanat ^® EP-M60 26 5 Comparative Example: Vestanat ^® EP-M120 53.2 6 Setalux ^® 1760 VB-64 (64% pure) 35.97 37.25 41,85 40.6 41.6 7 EP-CAT 11B 0.92 0.95 1.06 1.0 1.1 8th TegoGlide 410 (10% in butyl acetate) 0.50 0.49 0.48 0.49 0.5 9 Tinuvin 292 0.23 0.24 0.27 0.26 0.27 10 Tinuvin 900 (8% in xylene) 2.88 2.98 3.34 3.25 3.33 11 Butyl acetate / xylene (1: 1) 30.72 28.28 26.21 28.4 0

• Die zu bestimmende flüssige Probe (mind. 70ml) wird in ein 100ml Glasfläschchen gefüllt und mit einem Metallstift in senkrechter Ausrichtung versehen, an dessen Ende, welches in die Probe eintaucht, ein rundes Metallplättchen mit dem Durchmesser von ca. 2cm hängt. Das Glasfläschchen wird mit einem Lochdeckel versehen und der Metallstift in das Gelierzeitgerät (Techne Gelation Timer) eingespannt. Die Probe befindet sich jetzt in einem auf Zimmertemperatur (23°C) eingestelltem Wasserbecken (Lauda Thermostat Typ BK2). Der Metallstift in der Probe bewegt sich oszillierend in einem gleichbleibendem Rhythmus auf und ab, bis der Widerstand der Probe größer ist, als die Kraft des Gelierzeitgeräts. In diesem Fall bleibt der Metallstift stecken, die Probe ist "geliert". Die Zeitdauer zwischen Start der oszillierenden Bewegung des Metallstifts und Beendigung dieser, wird am Display des Geliergeräts angegeben.

Tabelle 2: Topfzeiten der Zusammensetzungen I-V Klarlacksystem Topfzeit (h) I 19,5 II 20,8 III (Vergleichsbeispiel) 4,3 IV (Vergleichsbeispiel) 4,0 V (Vergleichsbeispiel) 2,0 Table 2 shows the pot lives of compositions IV. The pot lives were determined as follows:

• The liquid sample to be determined (at least 70 ml) is filled into a 100 ml glass vial and fitted with a metal pin in a vertical orientation, at the end of which dips into the sample, a round metal plate with the diameter of about 2 cm hangs. The glass vial is provided with a hole lid and the metal pin is clamped in the gelling time device (Techne Gelation Timer). The sample is now in a water basin set at room temperature (23 ° C) (Lauda thermostat type BK2). The metal pin in the sample oscillates up and down in a constant rhythm until the resistance of the sample is greater than the force of the gelling timer. In this case, the metal pin sticks, the sample is "gelled". The time between the start of the oscillating movement of the metal pin and the completion of this, is indicated on the display of the gelling device.

<b> Table 2: Pot lives of compositions IV </ b> Clearcoat system Pot life (h) I 19.5 II 20.8 III (comparative example) 4.3 IV (comparative example) 4.0 V (comparative example) 2.0

It is clear from the pot lives shown in Table 2 that the alkoxysilane and allophanate-functionalized coating compositions I and II according to the invention have a significantly longer pot life than Comparative Examples III-V. From the prior art (Comparative Examples III-V) It is not to be expected that the pot life of the alkoxysilane- and allophanate-functionalized coating compositions I and II according to the invention which comprise the alkoxysilane- and allophanate-functionalized urethanes 1-2 according to the invention will be extended many times over.

Hardening of the clearcoats

To determine the mechanical characteristics, all varnishes of a 120 μm doctor blade were applied to phosphated steel sheets (Chemetall Gardobond 26S / 60 / OC) and cured at 160 ° C. for 22 minutes. <b> Table 3: Paint properties of alkoxysilane and allophanate-functionalized coating compositions I-III according to the invention after curing at 160 ° C. (22 min) </ b> composition I II III Pendulum hardness (king) [s] n 1 d 182 202 147 Erichsen cupping [mm] (EN ISO 1520) 6.0 6.5 4.5 MEK test [ASTM D 4752] (double strokes, 1 kg weight) > 150 > 150 > 150

The coating properties of the coatings which were obtained when using the alkoxysilane and allophanate-functionalized coating compositions I and II according to the invention show, compared with Comparative Example III, a high pendulum hardness coupled with exceptionally high flexibility and good MEK resistance.

Claims (26)

Alkoxysilane-functionalized and allophanate-functionalized coating compositions containing a) 10-99 wt .-% of at least one binder component from the reaction product of I. A) alkoxysilane-containing monourethanes A) of the formula 1

R _n (OR ¹ ) _3-n Si-R ² -NH- (C = O) -OR ³ Formula 1

wherein R _n , R ¹ , R ² and R ³ independently of one another are hydrocarbon radicals having 1-8 C atoms, which may be linear, branched or cyclic, or may also merge cyclically into one another, and n is 0-2,
and B) at least one diisocyanate B),
optionally in the presence of at least one catalyst K),
in a molar ratio of A) to B) of 1.0: 1.5 to 1.0: 0: 6, preferably 1.15: 1 to 0.85: 1, particularly preferably 1: 1. II. And the subsequent implementation C) with at least one diol and / or polyol C), optionally in the presence of at least one catalyst K),
in the ratio of the NCO groups of the reaction product I to the OH groups of the diol and / or polyol II. C) of 1.0: 1.5 to 1.0: 0: 6, preferably 1.15: 1 to 0 , 85: 1, more preferably 1: 1; b) 1-90% by weight of at least one binder component, preferably a hydroxyl-containing or amine-group-containing binder, c) 0-50% by weight of at least one aromatic, aliphatic or cycloaliphatic polyisocyanate which has an NCO functionality of at least 2, preferably 2.8 to 6, d) 0-5% by weight of at least one catalyst, wherein components a) -d) add up to 100% by weight, e) optional excipients and / or additive, f) optional solvent. Alkoxysilane-functionalized and allophanate-functionalized coating compositions consisting of a) 10-99 wt .-% of at least one binder component from the reaction product of I. A) alkoxysilane-containing monourethanes A) of the formula 1

R _n (OR ¹ ) _3-n Si-R ² -NH- (C = O) -OR ³ Formula 1

wherein R _n , R ¹ , R ² and R ³ independently of one another are hydrocarbon radicals having 1-8 C atoms, which may be linear, branched or cyclic, or may also merge cyclically into one another, and n is 0-2,
and B) at least one diisocyanate B),
optionally in the presence of at least one catalyst K),
in a molar ratio of A) to B) of 1.0: 1.5 to 1.0: 0: 6, preferably 1.15: 1 to 0.85: 1, more preferably 1: 1; II. And the subsequent implementation C) with at least one diol and / or polyol C), optionally in the presence of at least one catalyst K),
in the ratio of the NCO groups of the reaction product I to the OH groups of the diol and / or polyol II. C) of 1.0: 1.5 to 1.0: 0.6, preferably 1.15: 1 to 0 , 85: 1, more preferably 1: 1; b) 1-90% by weight of at least one binder component, preferably a hydroxyl-containing or amine-group-containing binder, c) 0-50% by weight of at least one aromatic, aliphatic or cycloaliphatic polyisocyanate which has an NCO functionality of at least 2, preferably 2.8 to 6, d) 0-5% by weight of at least one catalyst, wherein components a) -d) add up to 100% by weight, e) optional excipients and / or additive, f) optional solvent. Alkoxysilane-functionalized and allophanate-functionalized coating compositions according to Claim 1 or 2, in which R _n , R ¹ , R ² and R ^3, simultaneously or independently of one another, are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, or tert-butyl. Alkoxysilane-functionalized and allophanate-functionalized coating compositions according to at least one of the preceding claims, wherein n is 0, R ¹ and R ^{3 are the} same or independently of one another methyl or ethyl, and R ² simultaneously or independently of one another is methyl or propyl. Alkoxysilane-functionalized and allophanate-functionalized coating compositions according to at least one of the preceding claims, wherein n is 0 and R ² is methyl or propyl, and R ¹ is methyl or ethyl and R ³ = R ¹ . Alkoxysilane-functionalized and allophanate-functionalized coating compositions according to at least one of the preceding claims, wherein n is 0, R ¹ and R ³ are methyl and R ² is propyl. Alkoxysilane-functionalized and allophanate-functionalized coating compositions according to at least one of the preceding claims, wherein diisocyanates B) selected from isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 2,2 'dicyclohexylmethane diisocyanate (2,2'-H12MDI), 2,4' dicyclohexylmethane diisocyanate (2,4'-H12MDI), 4,4'-dicyclohexylmethane diisocyanate (4,4'-H12MDI), 2-methylpentane diisocyanate (MPDI), pentane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate (2,2,4-TMDI), 2,4,4-trimethylhexamethylene diisocyanate (2,4,4 TMDI), norbornane diisocyanate (NBDI), methylene diphenyl diisocyanate (MDI), toluidine diisocyanate (TDI), tetramethylxylylene diisocyanate (TMXDI), xylylene diisocyanate (MXDI), individually or mixtures thereof. Alkoxysilane-functionalized and allophanate-functionalized coating compositions according to at least one of the preceding claims, wherein diols C) and polyols C) selected from ethylene glycol, 1,2-, 1,3-propanediol, diethylene, dipropylene, triethylene, tetraethylene glycol, 1 , 2-, 1,4-butanediol, 1,3-butylethylpropanediol, 1,3-methylpropanediol, 1,5-pentanediol, bis (1,4-hydroxymethyl) cyclohexane (cyclohexanedimethanol), glycerol, hexanediol, neopentyl glycol, trimethylolethane, Trimethylolpropane, pentaerythritol, bisphenol A, B, C, F, norbornylene glycol, 1,4-benzyldimethanol, ethanol, 2,4-dimethyl-2-ethylhexane-1,3-diol, 1,4- and 2,3-butylene glycol , Di-β-hydroxyethylbutanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, decanediol, dodecanediol, neopentyl glycol, cyclohexanediol, 3 (4), 8 (9) -bis (hydroxymethyl) -tricyclo [ 5.2.1.0 ^2,6 ] decane (dicidol), 2,2-bis (4-hydroxycyclohexyl) propane, 2,2-bis [4- (β-hydroxyethoxy) -phenyl] propane, 2-methyl-propanediol 1,3, 2-methylpentanediol-1,5, 2,2,4 (2,4,4) -trimethylhexa 1,1-diol-1,6, hexanetriol-1,2,6, butanetriol-1,2,4, tris (β-hydroxyethyl) isocyanurate, mannitol, sorbitol, polypropylene glycols, polybutylene glycols, xylylene glycol or hydroxypivalic acid neopentyl glycol esters, alone or in mixtures , Alkoxysilane-functionalized and allophanate-functionalized coating compositions according to claims 1-5, wherein diols C) and polyols C) selected from ethylene glycol, triethylene glycol, 1,4-butanediol, 1,2-propanediol, 1,5-pentanediol, 1,6- Hexanediol, cyclohexanedimethanol, decanediol, 1,12-dodecanediol, 2,2,4-trimethylhexanediol-1,6, 2,4,4-trimethylhexanediol-1,6, 2,2-dimethyl-1,3-butanediol, 2- Methyl-pentanediol-2,4, 3-methyl-pentanediol-2,4, 2,2,4-trimethyl-pentanediol-1,3, 2-ethylhexanediol-1,3, 2,2-dimethyl-1,3-hexanediol, 3 Methyl pentanediol-1,5, 2-methylpentanediol-1,5, trimethylolpropane, 2,2-dimethylpropanediol-1,3 (neopentyl glycol), hydroxypivalic acid neopentyl glycol ester and cis / trans-1,4-cyclohexanediol, alone or in mixtures , Alkoxysilane-functionalized and allophanate-functionalized coating compositions according to Claims 1-5, where diols C) and polyols C) are selected from 1,5-pentanediol, 1,6-hexanediol, 1,12-dodecanediol, 2,2,4-trimethylhexanediol 1,6, 2,4,4-trimethylhexanediol-1,6, 2,2-dimethyl-1,3-butanediol, 2-methyl-pentanediol-2,4, 3-methylpentanediol-2,4, 2, 2,4-trimethylpentanediol-1,3, 2-ethylhexanediol-1,3,2,2-dimethylhexanediol-1,3,3-methylpentanediol-1,5, 2-methylpentanediol-1,5, 2, 2-dimethylpropanediol-1,3 (neopentyl glycol) and cis / trans-1,4-cyclohexanediol, alone or in mixtures. Alkoxysilane-functionalized and allophanate-functionalized coating compositions according to at least one of the preceding claims, characterized in that as diols C) and polyols C) hydroxyl-containing polyesters, polyethers, polyacrylates, polycarbonates and polyurethanes having an OH number of 20 to 500 mg KOH / g and an average molecular weight of 250 to 6000 g / Mole, alone or in mixtures. Alkoxysilane-functionalized and allophanate-functionalized coating compositions according to at least one of the preceding claims, characterized in that as diols C) and polyols C) hydroxyl-containing polyesters or polyacrylates having an OH number of 50 to 250 mg KOH / g and an average molecular weight of 500 to 6000 g / mol, alone or in mixtures. Alkoxysilane-functionalized and allophanate-functionalized coating compositions, characterized in that as catalyst K) metal carboxylates, tertiary amines, amidines guanidines, quaternary ammonium salts, Tetralkylammoniumsalze, quaternary phosphonium salts, Metallacetylacetonate quaternary Ammoniumacetylacetonate quaternary Phosphoniumacetylacetonate, carboxylic acids, aluminum, zirconium, titanium - And / or boron alcoholates and / or esters thereof, phosphorus and nitrogen-containing catalyst, sulfonic acids, alone or in mixtures used. Alkoxysilane-functionalized and allophanate-functionalized coating compositions, characterized in that as catalyst K) zinc acetylacetonate and / or zinc ethylhexanoate is used. Alkoxysilane-functionalized and allophanate-functionalized coating compositions according to at least one of the preceding claims, characterized in that as binders b) a hydroxyl-containing and / or amine-group-containing binder is used. Alkoxysilane-functionalized and allophanate-functionalized coating compositions according to at least one of the preceding claims, characterized in that as binders b) hydroxyl-containing polyesters, polyethers, polyacrylates, polycarbonates and polyurethanes having an OH number of 20 to 500 mg KOH / g and an average molecular weight from 250 to 6000 g / mole, alone or in mixtures. Alkoxysilane-functionalized and allophanate-functionalized coating compositions according to at least one of the preceding claims, characterized in that as binders b) hydroxyl-containing polyesters or polyacrylates having an OH number of 50 to 250 mg KOH / g and an average molecular weight of 500 to 6000 g / mol are used as binder components, alone or in mixtures. Alkoxysilane-functionalized and allophanate-functionalized coating compositions according to at least one of the preceding claims, characterized in that as binder b) at least one adduct of an isocyanatotrialkyoxysilane and a mono- or polyhydric alcohol is contained. Alkoxysilane-functionalized and allophanate-functionalized coating compositions according to at least one of the preceding claims, characterized in that the binder b) is at least one derivative of hydroxyl-containing polyethers, polyesters, polycarbonate diols or polyacrylates with isocyanatopropyltrialkoxysilane, alone or in mixtures. Alkoxysilane-functionalized and allophanate-functionalized coating compositions according to at least one of the preceding claims, characterized in that as binder b), aminopropyltriethoxysilane, aminomethyltrimethoxysilane or aminomethyltriethyoxysilane, alone or in mixtures, is contained. Alkoxysilane-functionalized and allophanate-functionalized coating compositions according to at least one of the preceding claims, characterized in that as component c) polyisocyanates selected from isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 2,2 'di-cyclohexylmethane diisocyanate (2,2'-H12MDI ), 2,4'-dicyclohexylmethane diisocyanate (2,4'-H12MDI), 4,4'-dicyclohexylmethane diisocyanate (4,4'-H12MDI), 2-methylpentane diisocyanate (MPDI), pentane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate (2,2,4 -TMDI), 2,4,4-trimethylhexamethylene diisocyanate (2,4,4 TMDI), norbornane diisocyanate (NBDI), methylene diphenyl diisocyanate (MDI), toluidine diisocyanate (TDI), tetramethylxylylene diisocyanate (TMXDI), xylylene diisocyanate (MXDI), individually or mixtures thereof become. Alkoxysilane-functionalized and allophanate-functionalized coating compositions according to at least one of the preceding claims, characterized in that are used as component c) isocyanurates, in particular from IPDI and / or HDI. Alkoxysilane-functionalized and allophanate-functionalized coating compositions according to at least one of the preceding claims, characterized in that as catalysts d) metal carboxylates, tertiary amines, amidines guanidines, quaternary ammonium salts, Tetralkylammoniumsalze, quaternary phosphonium salts, Metallacetylacetonate, quaternary Ammoniumacetylacetonate quaternary Phosphoniumacetylacetonate, carboxylic acids, Aluminum, zirconium, titanium and / or boron alcoholates and / or esters thereof, phosphorus and nitrogen-containing catalyst, sulfonic acids, alone or in mixtures, are used. Alkoxysilane-functionalized and allophanate-functionalized coating compositions according to at least one of the preceding claims, characterized in that catalysts d) selected from tetraethylammonium benzoate, tetrabutylammonium hydroxide, tetraethylammonium acetylacetonate, tetrabutylammonium acetylacetonate, dibutyltin dilaurate, zinc acetylacetonate, zinc ethylhexanoate. Alkoxysilane-functionalized and allophanate-functionalized coating compositions according to at least one of the preceding claims, characterized in that as additives E) solvents, stabilizers, light stabilizers, additional crosslinkers, fillers, pigments, leveling agents or rheology aids, alone or in mixtures, are used. Use of the alkoxysilane-functionalized allophanate-containing coating compositions according to at least one of the preceding claims in coating compositions, adhesive compositions, sealant compositions and metal coating compositions.